Perovskite compositions comprising mixed solvent systems

Abstract

Described herein is an ink solution, comprising a composition of formula (I): ABX 3 (I), wherein A comprises at least one cation selected from the group consisting of methylammonium, tetramethylammonium, formamidinium, cesium, rubidium, potassium, sodium, butylammonium, phenethylammonium, phenylammonium, and guanidinium; B comprises at least one divalent metal; and X is at least one halide; and a mixed solvent system comprising two or more solvents selected from the group consisting of dimethyl sulfoxide, dimethylformamide, γ-butyrolactone, 2-methoxyethanol, and acetonitrile. Methods for producing poly-crystalline perovskite films using the ink solutions described herein and the use of the films in photovoltaic and photoactive applications are additionally described.

What is claimed is: 
     
         1 . An ink solution, comprising a composition of formula (I):
   ABX 3   (I)
   wherein A comprises at least one cation selected from the group consisting of methylammonium, tetramethylammonium, formamidinium, cesium, rubidium, potassium, sodium, butylammonium, phenethylammonium, phenylammonium, and guanidinium;   B comprises at least one divalent metal; and   X is at least one halide; and   a mixed solvent system comprising two or more solvents selected from the group consisting of dimethyl sulfoxide, dimethylformamide, γ-butyrolactone, 2-methoxyethanol, and acetonitrile.   
     
     
         2 . The ink solution of  claim 1 , further comprising a compound of BX′ 2  wherein B is a least one divalent metal and X′ is a monovalent anion; a compound of formula AX, wherein A is at least one monovalent cation selected from the group consisting of methylammonium, tetramethylammonium, formamidinium, guanidinium, cesium, rubidium, potassium, sodium, butylammonium, phenethylammonium, and phenylammonium; and X is selected from the group consisting of halide, acetate (CH 3 CO 2   − ), and thiocyanate (SCN − ). 
     
     
         3 . The ink solution of  claim 2 , wherein the relative amount of ABX 3  to BX′ 2  and AX is about 99:1. 
     
     
         4 . The ink solution of  claim 1 , wherein said two or more solvents are acetonitrile and 2-methoxyethanol. 
     
     
         5 . The ink solution of  claim 1 , wherein said mixed solvent system comprises one or more coordinating solvents selected from the group consisting of dimethyl sulfoxide and dimethylformamide and one or more solvents selected from the group consisting of γ-butyrolactone, 2-methoxyethanol, and acetonitrile. 
     
     
         6 . The ink solution of  claim 5 , wherein the coordinating solvent is present in an amount of about 0.01 to 10.0% by volume. 
     
     
         7 . The ink solution of  claim 6 , wherein the coordinating solvent is dimethyl sulfoxide. 
     
     
         8 . The ink solution of  claim 1 , wherein said mixed solvent system is a ternary mixed solvent system comprising acetonitrile, 2-methoxyethanol, and dimethyl sulfoxide. 
     
     
         9 . The ink solution of  claim 8 , wherein said ternary mixed solvent system comprises 95-99.9% by volume acetonitrile and 2-methoxyethanol and 0.1-5% by volume dimethyl sulfoxide. 
     
     
         10 . The ink solution of  claim 1 , wherein the composition of Formula (I) is selected from the group consisting of cesium lead iodide (CsPbI 3 ), methylammonium tin iodide (CH 3 NH 3 SnI 3 ), cesium tin iodide (CsSnI 3 ), methylammonium lead iodide (CH 3 NH 3 PbI 3 ), cesium lead bromide (CsPbBr 3 ), methylammonium tin bromide (CH 3 NH 3 SnBr 3 ), cesium tin bromide (CsSnBr 3 ), methylammonium lead bromide, (CH 3 NH 3 PbBr 3 ), formamidinium tin bromide (CHNH 2 NH 2 SnBr 3 ), formamidinium lead bromide (CHNH 2 NH 2 PbBr 3 ), formamidinium tin iodide (CHNH 2 NH 2 SnI 3 ), and formamidinium lead iodide (CHNH 2 NH 2 PbI 3 ). 
     
     
         11 . The ink solution of  claim 10 , wherein the composition of Formula (I) is methylammonium lead iodide (CH 3 NH 3 PbI 3 ). 
     
     
         12 . The ink solution of  claim 1 , wherein said at least one divalent metal (B) is selected from the group consisting of lead, tin, cadmium, germanium, zinc, nickel, platinum, palladium, mercury, titanium, and silicon. 
     
     
         13 . The ink solution of  claim 1 , wherein said at least one divalent metal (B) is lead or tin. 
     
     
         14 . The ink solution of  claim 1 , wherein said divalent metal (B) is lead. 
     
     
         15 . The ink solution of  claim 1 , further comprising a partial substitution of (B) by a metal selected from the group consisting of lithium, sodium, potassium, cesium, rubidium, magnesium, calcium, strontium, barium, antimony, bismuth, arsenic, phosphorus, gallium, indium, thallium, molybdenum, gold, silver, copper, and combinations thereof. 
     
     
         16 . The ink solution of  claim 2 , wherein said monovalent anion (X′) is selected from the group consisting of halide, acetate (CH 3 CO 2 ), and thiocyanate (SCIS). 
     
     
         17 . The ink solution of  claim 2 , wherein said compound of the formula BX′ 2  is selected from the group consisting of PbI 2 , PbBr 2 , PbCl 2 , Pb(CH 3 CO 2 ) 2 , SnI 2 , SnBr 2 , SnCl 2 , and Sn(CH 3 CO 2 ) 2 . 
     
     
         18 . The ink solution of  claim 17 , wherein said compound of the formula BX′ 2 is PbI 2 . 
     
     
         19 . The ink solution of  claim 2 , wherein the compound of formula AX is selected from the group consisting of methylammonium iodide, methylammonium bromide, methylammonium chloride, formamidinium iodide, formamidinium bromide, formamidinium chloride, cesium iodide, cesium bromide, cesium chloride, butylammonium iodide, butylammonium bromide, butylammonium chloride, phenethylammonium iodide, phenethylammonium bromide, phenethylammonium chloride, phenylammonium iodide, phenylammonium bromide, and phenylammonium chloride. 
     
     
         20 . The ink solution of  claim 19 , wherein the compound of formula AX is selected from the group consisting of methylammonium iodide, cesium iodide, formamidinium iodide, butylammonium iodide, phenethylammonium iodide, methylammonium bromide, cesium bromide, formamidinium bromide, butylammonium bromide, and phenethylammonium iodide. 
     
     
         21 . The ink solution of  claim 20 , wherein the compound of formula AX is methylammonium iodide. 
     
     
         22 . The ink solution of  claim 1 , further comprising a partial substitution of (A) by a metal selected from the group consisting of lithium, magnesium, calcium, strontium, barium, and combinations thereof. 
     
     
         23 . The ink solution of  claim 2 , wherein BX′ 2  is PbI 2  and AX is methylammonium iodide. 
     
     
         24 . The ink solution of  claim 1  having a vapor pressure in a range of about 5 to 100 kPa, for use in a fast coating process, wherein said fast coating process is selected from the group consisting of blade coating, slot die coating, shear coating, gravure coating, brush coating, syringe coating, and screen printing. 
     
     
         25 . A method for producing a polycrystalline perovskite film using the ink solution of  claim 1 , said method comprising:
 contacting said ink solution of  claim 1  using a fast coating process onto a substrate to form a film, wherein said fast coating process is selected from the group consisting of blade coating, slot die coating, shear coating, gravure coating, brush coating, syringe coating, and screen printing.   
     
     
         26 . The method of  claim 25 , wherein said contacting of the ink solution onto said substrate using said fast coating process is conducted at about 2 to about 10,000 mm/s. 
     
     
         27 . The method of  claim 26 , wherein said contacting of the ink solution onto said substrate using said fast coating process is conducted at about 40 mm/s. 
     
     
         28 . The method of  claim 26 , wherein said contacting of the ink solution onto said substrate using said fast coating process is conducted at about 99 mm/s. 
     
     
         29 . The method of  claim 25 , further comprising annealing said film, wherein a polycrystalline perovskite film having large grain sizes of about 10 nm to 1 mm is prepared. 
     
     
         30 . The method of  claim 25 , wherein the area of the film produced is at least 25 cm 2 . 
     
     
         31 . A film comprising a polycrystalline perovskite composition of formula (I):
   ABX 3   (I)
   
       wherein A comprises at least one cation selected from the group consisting of methylammonium, tetramethylammonium, formamidinium, cesium, rubidium, potassium, sodium, butylammonium, phenethylammonium, phenylammonium, and guanidinium;
 B comprises at least one divalent metal; and 
 X is at least one halide; 
 wherein the film of said polycrystalline perovskite composition has large grain sizes in a range of about 10 nm to 1 mm, a thickness in a range of about 10 nm to 1 cm, and a compact, pin-hole free, and uniform structure of at least 25 cm 2 . 
 
     
     
         32 . The film of  claim 31 , wherein the crystalline perovskite composition of Formula (I) is selected from the group consisting of cesium lead iodide (CsPbI 3 ), methylammonium tin iodide (CH 3 NH 3 SnI 3 ), cesium tin iodide (CsSnI 3 ), methylammonium lead iodide (CH 3 NH 3 PbI 3 ), cesium lead bromide (CsPbBr 3 ), methylammonium tin bromide (CH 3 NH 3 SnBr 3 ), cesium tin bromide (CsSnBr 3 ), methylammonium lead bromide, (CH 3 NH 3 PbBr 3 ), formamidinium tin bromide (CHNH 2 NH 2 SnBr 3 ), formamidinium lead bromide (CHNH 2 NH 2 PbBr 3 ), formamidinium tin iodide (CHNH 2 NH 2 SnI 3 ), and formamidinium lead iodide (CHNH 2 NH 2 PbI 3 ). 
     
     
         33 . The film of  claim 32 , wherein the crystalline perovskite composition of Formula (I) is methylammonium lead iodide (CH 3 NH 3 PbI 3 ). 
     
     
         34 . A solar cell, solar panel, light emitting diode, photodetector, x-ray detector, field effect transistor, memristor, or synapse comprising the polycrystalline perovskite film of  claim 31 . 
     
     
         35 . A perovskite solar cell, comprising:
 a substrate;   a first transport layer disposed on said substrate;   the film of  claim 31  disposed on said first transport layer;   a second transport layer disposed on said film; and   a conductive electrode disposed on said second transport layer.   
     
     
         36 . A photovoltaic module comprising a plurality of solar cells of  claim 35 , wherein said module exhibits a Power Conversion Efficiency of at least 12%. 
     
     
         37 . The photovoltaic module of  claim 36 , wherein said module exhibits a Power Conversion Efficiency of at least 13%. 
     
     
         38 . The photovoltaic module of  claim 36 , wherein said module exhibits a Power Conversion Efficiency of at least 14%. 
     
     
         39 . The photovoltaic module of  claim 36 , wherein said module exhibits a Power Conversion Efficiency of at least 15%.